1. Field of the Invention
The present invention relates to a novel perfluoroalkylated aniline derivative, which is a useful intermediate, to an industrially advantageous novel process for producing the aniline derivative and to a novel aniline derivative, which is also a useful intermediate, derived from the said derivative.
Perfluoroalkylated aniline derivatives are useful as intermediates or raw materials for the synthesis of agricultural chemicals, pharmaceuticals, surface active agents, rubber materials, mold release agents, water and oil repellents, optical materials, gas separation membrane materials, resist materials, antifouling paints, weatherproofing paints, paper-converting agents, textile-treating agents, heat resistant resins, etc. (cf, for example, xe2x80x9cSaisentan Gijutsu (Advanced Technologies) in Halogen Chemicalsxe2x80x9d, published by CMC); for use in agricultural chemicals, in particular, they are useful compounds as raw materials for the agricultural and horticultural insecticides disclosed in EP 919542. With regard to perfluoroalkylanilines, however, virtually no simple and useful process for the production thereof has hitherto been reported.
The present invention provides a novel process for producing perfluoroalkylated, paticularly secondary perfluoroalkylated aniline derivatives and novel, useful intermediates which can be produced by the process.
2. Related Art Statement
Known processes for producing perfluoroalkylated aniline derivatives include, for example, [A] a method which comprises introducing a perfluoroalkyl group by replacing the halogen atom of a halogenated nitrobenzene and then reducing the nitro group into the amino group and a method which comprises introducing a perfluoroalkyl group by replacing the halogen atom of a halogenated aniline. The following processes have been reported with regard to producing perfluoroalkylated aniline derivatives according to either of the above-mentioned methods.
(a) Processes wherein the reaction is conducted by using a perfluoroalkyl halide as the perfluoroalkylating agent in the presence of metallic copper are described, for example, in (1) Tetrahedron, 1969, 25, 5921, (2) Offenlegungsschrift 26 06 982, (3) J. Chem. Soc. Japan, 1972, 1876, (4) J. Chem. Soc. Perkin Trans. 1, 1980, 661, and (5) Bull. Chem. Soc. Jpn., 1992, 65, 2141. These processes, however, are industrially disadvantageous in that previous introduction of a halogen to an appropriate position of a nitrobenzene or an aniline is necessary, excess of copper is required, and further the reaction temperature is unfavorably high.
(b) Processes wherein the reaction is conducted by using a perfluoroalkylcarboxylic acid metal salt as the perfluoroalkylating agent in the presence of copper iodide are described, for example, in (1) J. Chem. Soc. Perkin Trans, 1, 1988, 921 and (2) Synth. Commun., 1988, 18, 965. These processes are also industrially disadvantageous in that they require a nitrobenzene having a halogen atom introduced to its appropriate position, it needs a large amount of copper iodide, and the reaction temperature is unfavorably high.
(c) A process wherein the reaction is conducted by using a perfluoroalkyltrialkylsilane as the perfluoroalkylating agent in the presence of potassium fluoride and copper iodide is described, for example, in (1) Tetrahedron Lett., 1991, 32, 91. This process also is industrially unsuitable in that it requires a nitrobenzene having a halogen atom introduced to its appropriate position, the perfluoroalkylating agent is expensive and the use of stoichiometric amounts of potassium fluoride and copper iodide is necessary.
(d) Processes wherein a perfluoroalkene is made to react on a fluoronitrobenzene in the presence of fluorine anions are described, for example, in (1) J. Chem. Soc. (c), 1968, 2221, (2) J. Org. Synth Chem. Japan, 1969, 27, 993, (3) J. Chem. Soc. Japan, 1976, 198 and (4) Tetrahedron, 1995, 51, 13167. These processes are not suitable for general use because the substrates which can be used are restricted to those compounds which have been strongly activated by an electron attractive groups, e.g., perfluoronitrobenzenes and dinitrofluorobenzenes and hence the compounds which can be prepared by these processes are greatly restricted in their structure.
[B] The following have been reported as to the method of directly perfluoroalkylating an aniline.
(a) Processes wherein a perfluoroalkyl halide is made to react on an aniline in the presence of a reducing agent are described, for example, in (1) EP 298,803 (JP-A-1-100135), (2) EP 206,951 (JP-A-62-26241), (3) J. Chem. Soc. Perkin Trans., 1, 1990, 2293, (4) J. Chem. Soc., Chem. Commun., 1987, 1701 and (5) J. Heterocyclic Chem., 1994, 31, 1413. In these processes, the yield of the intended product is low to medium and the selectivity is very poor as to the position to be perfluoroalkylated, hence they cannot be expected to be useful in practice.
(b) A process wherein the perfluoroalkylated compound is irradiated with light in the presence of a reducing agent is disclosed, for example in JP-A-57-18638. This process also gives a low to medium yield of the product and a very poor selectivity, and hence presents a low practical usefulness.
(c) Processes wherein a perfluoroalkyl halide or a perfluoroalkylsulfonyl chloride is heated in the presence of a metal catalyst are described, for example, in (1) J. Fluorine Chem., 1983, 22, 541, (2) JP-A-57-142923, (3) WO 93/16969 (Jap. Nat. Publ. (Kohyo) 7-504414, U.S. Pat. No. 5,276,194), (4) JP-A-3-240739 and (5) EP-0, 114,359. Among these, the processes of (1) and (2) give a low to medium yield, show a low selectivity, require a large amount of copper, need a high temperature and long reaction time, and thus are industrially disadvantageous. The process of (3) has the disadvantages of requiring an expensive catalyst and high reaction temperature and showing substantially no selectivity. The processes of (4) and (5) cannot be expected to be useful in practice because they require an expensive catalyst, high temperature and long time and moreover no embodiment treating an aniline is described.
(d) Processes wherein the peroxide of a perfluoroalkylcarboxylic acid is used are described, for example, in (1) JP-A-3-109362, (2) JP-A-5-246933, and (3) Bull. Chem. Soc. Jpn., 1995, 68, 1042. These processes, however, are disadvantageous in that they require the use of a hazardous peroxide and the substrate to be used is restricted to phenylenediamines or quinones and hence they are not suited to general use.
(e) A process wherein a perfluoroalkylhalide is treated under a high temperature and an applied pressure is described in U.S. Pat. No. 3,281,426, but the process is industrially disadvantageous in that it require a high temperature and a special apparatus.
(f) Processes wherein a perfluoroalkylcarboxylic acid is treated with xenon difluoride are described, for example, in (1) J. Org. Chem., 1988, 53, 4582, and (2) JP-A-6-184065. These processes have the disadvantages in that they require a large amount of highly toxic reagent and both the yield and the selectivity are not sufficiently high.
An object of the present invention is, overcomming the above-mentioned various problems of the prior techniques, to provide a process for producing a perfluoroalkyl-substituted aniline which uses raw materials, reagents and catalysts which are inexpensive, easily available, safe and easy to handle, is based on reactions which are mild, simple and give a high yield and selectivity, does not produce a large amount of wastes and is economically highly efficient also in the aftertreatment. Another object of the present invention is to provide a novel perfluoroalkylated aniline derivative, particularly a secondary perfluoroalkylated aniline derivative, which can be used for versatile and valuable applications.
The present inventions have made are extensive study to solve the above-mentioned problems and resultantly found a novel process for production and a novel intermediate compound which can be obtained by the process.
According to the present invention, there are provided an aniline derivative represented by the formula (I) 
wherein R1 and R2 may be the same or different and each denote a hydrogen atom, (C1-12)alkyl group, (C3-8)cycloalkyl group, hydroxy(C1-12) alkyl group, hydroxycarbonyl(C1-2) alkyl group, (C1-6)alkoxycarbonyl(C1-6) alkyl group, xe2x80x94COR8 (wherein R8 is a hydrogen atom, (C1-12)alkyl group, halo(C1-12)alkyl group, (C3-8)cycloalkyl group, phenyl group or phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, hydroxyl group, halogen atom, (C1-6) alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group) or COOR9 (wherein R9 is a (C1-6)alkyl group, halo(C1-6)alkyl group, phenyl group, phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, hydroxyl group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6) alkoxy group, halo(C1-6) alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group, benzyl group or benzyl group substituted on the ring with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, hydroxyl group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxy-carbonyl group);
R3, R4, R5, R6 and R7 may be the same or different and each denote a hydrogen atom, halogen atom, hydroxyl group, nitro group, (C1-12)alkyl group, halo(C1-12)alkyl group, (C1-12)alkoxy group, halo(C1-12)alkoxy group, (C1-12)alkylthio group, halo(C1-12)alkylthio group, (C1-6)alkylthio (C1-6)alkyl group, hydroxy (C1-6)alkyl group, amino (C1-6)alkyl group, amino(C1-6)alkyl group substituted with one or two (C1-6)alkyl groups which may be the same or different, phenyl group, phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group and halo(C1-6)alkoxy group, phenoxy group, phenoxy group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group and halo(C1-6)alkoxy group, benzyl group, benzyl group substituted on the ring with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group and halo(C1-6)alkoxy group, xe2x80x94N(R10)R11 (wherein R10 and R11 may be the same or different and are each a hydrogen atom, (C1-12)alkyl group, (C3-8)cycloalkyl group, phenyl group, phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, hydroxyl group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group, benzyl group, benzyl group substituted on the ring with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, hydroxyl group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group, xe2x80x94COR8 wherein R8 has the same meaning as defined above, or COOR9 wherein R9 has the same meaning as defined above, further, R10 and R11 may conjointly from a (C3-6)alkylene group) or (C2-27)perfluoroalkyl group;
and further, R1 or R2 and R3 or R7 may conjointly form a (C2-4)alkylene group, and R3, R4, R5, R6 and R7 may form, with their two adjacent substituents joined together, a (C3-5)alkylene group or (C1-2)alkylenedioxyl group, and at least one of R3, R4, R5, R6 and R7 must be a (C2-27)-perfluoroalkyl group; provided that
(1) when R1, R2, R4 and R7 are each a hydrogen atom, R3 is a fluorine atom and R6 is a hydrogen atom, fluorine atom or chlorine atom, or when R1, R2, R3 and R6 are each a hydrogen atom, R7 is a fluorine atom and R4 is a hydrogen atom, fluorine atom or chlorine atom, then R5 must not be a pentafluoroethyl group or heptafluoro-n-propyl group,
(2) when R1 and R2 are each a hydrogen atom, R3 is a methyl group and R4, R6 and R7 are simultaneously each a hydrogen atom, or when R1 and R2 are each a hydrogen atom, R7 is a methyl group and R3, R4 and R6 are simultaneously each a hydrogen atom, then R5 must not be a pentafluoroethyl group, heptafluoropropyl group, nonafluoro-n-butyl group or nonafluoro-sec-butyl group,
(3) when R1 and R2 are each a hydrogen atom, R3 is a methyl group and R5, R6 and R7 are simultaneously each a hydrogen atom, or when R1 and R2 are each a hydrogen atom, R3, R5 and R6 are simultaneously each a hydrogen atom and R7 is a methyl group, then R4 must not be a pentafluoroethyl group,
(4) when R1 and R2 are each a hydrogen atom, R3 is a methyl group and R4, R5 and R7 are simultaneously each a hydrogen atom, then R6 must not be a pentafluoroethyl group; or when R1 and R2 are each a hydrogen atom, R3, R5 and R6 are simultaneously each a hydrogen atom and R7 is a methyl group, then R4 must not be a pentafluoroethyl group,
(5) when R1, R2, R4, R6 and R7 are simultaneously each a hydrogen atom and R3 is a chlorine atom or when R1, R2, R3, R4 and R6 are simultaneously each a hydrogen atom and R7 is chlorine atom, then R5 must not be a pentafluoroethyl group, heptafluoropropyl group or nonafluoro-n-butyl group,
(6) when R1, R2, R4, R6 and R7 are simultaneously each a hydrogen atom and R3 is an ethyl group, n-butyl group, methoxy group or trifluoromethyl group or when R1, R2, R3, R4 and R6 are simultaneously each a hydrogen atom and R7 is an ethyl group, n-butyl group, methoxy group or trifluoromethyl group, then R5 must not be a pentafluoroethyl group,
(7) when R1 and R2 are each a hydrogen atom and any four of the R3, R4, R5, R6 and R7 are simultaneously each a hydrogen atom, then the remaining one of the R3, R4, R5, R6 and R7 must not be a heptafluoroisopropyl group,
(8) when R1 and R2 are each a methyl group and R3, R4, R6 and R7 are simultaneously each a hydrogen atom, then R5 must not be a heptafluoroisopropyl group,
(9) when R1 and R2 are each a methyl group and R3, R5, R6 and R7 are simultaneously each a hydrogen atom, then R4 must not be a heptafluoroisopropyl group,
(10) when R1 and R2 are each a methyl group and R3, R4, R5 and R7 are simultaneously each a hydrogen atom, then R6 must not be a heptafluoroisopropyl group,
(11) when R1, R2, R3 and R6 are simultaneously each a hydrogen atom, R4 is an amino group and one of the R5 and R7 is a hydrogen atom, or when R1, R2, R4 and R7 are simultaneously each a hydrogen atom, R6 is an amino group and one of the R3 and R5 is a hydrogen atom, then the other of the two must not be a heptafluoroisopropyl group,
(12) when R1, R2, R4, R5 and R7 are simultaneously each a hydrogen atom and R6 is a methoxy group or iodine atom, then R3 must not be a heptafluoroisopropyl group, and
(13) when R1, R2, R3, R5 and R6 are simultaneously each a hydrogen atom and R4 is a methoxy group or iodine atom, then R7 must not be a heptafluoroisopropyl group,
and a process for producing an aniline derivative represented by the formula (Ixe2x80x2) 
wherein R1 and R2 are the same as defined below for the formula (III), and R3xe2x80x2, R4xe2x80x2, R5xe2x80x2, R6xe2x80x2 and R7xe2x80x2 may be the same or different and each denote a hydrogen atom, halogen atom, hydroxyl group, nitro group, (C1-12)alkyl group, halo(C1-12)alkyl group, (C1-12)alkoxy group, halo(C1-12)alkoxy group, (C1-12)alkylthio group, halo(C1-12)alkylthio group, (C1-6)alkylthio(C1-6)alkyl group, hydroxy(C1-6)alkyl group, amino(C1-6)alkyl group, amino(C1-6)alkyl group substituted with one or two (C1-6)alkyl groups which may be the same or different, phenyl group, phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group and halo(C1-6)alkoxy group, phenoxy group, phenoxy group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group and halo(C1-6)alkoxy group, benzyl group, benzyl group substituted on the ring with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group and halo(C1-6)alkoxy group, xe2x80x94N(R10)R11 (wherein R10 and R11 are the same as defined below for the formula (III)) or (C1-27)perfluoroalkyl group, and at least one of the R3xe2x80x2, R4xe2x80x2, R5xe2x80x2, R6xe2x80x2 and R7xe2x80x2 must be a (C1-27)perfluoroalkyl group,
which comprises allowing an iodide represented by the formula (II)
Ixe2x80x94R12xe2x80x83xe2x80x83(II) 
wherein R12 is a (C1-27)perfluoroalkyl group, to react with an aniline represented by the formula (III) 
wherein R1 and R2 may be the same or different and each denote a hydrogen atom, (C1-12)alkyl group, (C3-8)cycloalkyl group, hydroxy(C1-12)alkyl group, hydroxycarbonyl(C1-12)alkyl group, (C1-6)alkoxycarbonyl(C1-6)alkyl group, xe2x80x94COR8 (wherein R8 is a hydrogen atom, (C1-12)alkyl group, halo(C1-12)alkyl group, (C3-8)cycloalkyl group, phenyl group or phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, hydroxyl group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group) or COOR9 (wherein R9 is a (C1-6)alkyl group, halo(C1-6)alkyl group, phenyl group, phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxy-carbonyl group, benzyl group or benzyl group substituted on the ring with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group);
R13, R14, R15, R16 and R17 may be the same or different and such denote a hydrogen atom, halogen atom, hydroxyl group, nitro group, (C1-12)alkyl group, halo(C1-12)alkyl group, (C1-12)alkoxy group, halo(C1-12)alkoxy group, (C1-12)alkylthio group, halo-(C1-12)alkylthio group, (C1-6)alkylthio (C1-6)alkyl group, hydroxy(C1-6)alkyl group, amino(C1-6)alkyl group, amino-(C1-6)alkyl group substituted with one or two (C1-6)alkyl groups which may be the same or different, phenyl group, phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group and halo(C1-6)alkoxy group, phenoxy group, phenoxy group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group and halo(C1-6)alkoxy group, benzyl group, benzyl group substituted on the ring with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group and halo(C1-6)alkoxy group, or xe2x80x94N(R10)R11 (wherein R10 and R11 may be the same or different and are each a hydrogen atom, (C1-12)alkyl group, (C3-8)cycloalkyl group, phenyl group, phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, hydroxyl group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group, benzyl group, benzyl group substituted on the ring with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, hydroxyl group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxy-carbonyl group, xe2x80x94COR8 (wherein R8 is a hydrogen atom, (C1-12)alkyl group, halo(C1-12)alkyl group, (C3-8)cycloalkyl group, phenyl group or phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, hydroxyl group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group) or COOR9(wherein R9 is a (C1-6)alkyl group, halo(C1-6)alkyl group, phenyl group, phenyl group substituted with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group, benzyl group, or benzyl group substituted on the ring with 1-5 groups, which may be the same or different, selected from the group consisting of cyano group, nitro group, halogen atom, (C1-6)alkyl group, halo(C1-6)alkyl, group, (C1-6)alkoxy group, halo(C1-6)alkoxy group, carboxyl group and (C1-6)alkoxycarbonyl group), further, R10 and R11 may conjointly form a (C3-8)alkylene group); and further, R1 or R2 and R13 or R17 may conjointly form a (C2-4)alkylene group and R13, R14, R15, R16 and R17 may form, with their adjacent two substituents joined together, a (C3-5) alkylene group or (C1-2)alkylenedioxy group, in the presence of a reaction initiating agent.
The aniline derivatives referred to in the present invention includes those which are obtained directly by the above-mentioned reaction and those which are obtained by further modifying the aniline derivative thus formed, both of which are useful as intermediates for a variety of uses.
The process according to the present invention relates to a process for converting the hydrogen atom on the benzene ring of an aniline into a perfluoroalkyl group. The present invention relates to a process which exhibits a high selectivity to the perfluoroalkyl group introduction position for specific combinations of the substituents of the starting material aniline. However, the introduction position may vary according to the substituents of the anilines of the starting material and to the reaction conditions. Therefore, as a whole, the introduction site of the substituent is not restricted to a specific position alone.
In the description of the compounds in the present invention, in the definition of the respective substituents, xe2x80x9cixe2x80x9d means iso-, xe2x80x9csec-xe2x80x9d means secondary-, and xe2x80x9ct-xe2x80x9d means tertiary-; the xe2x80x9calkyl groupxe2x80x9d or xe2x80x9calkylxe2x80x9d, which represents the alkyl moiety, may be either of a straight chain or of a branched chain unless otherwise defined; the xe2x80x9c(C1-12)alkyl groupxe2x80x9d refers to an alkyl group having 1-12 carbon atoms and may be, for example, the methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, 1,2-dimethylpropyl group, hexyl group, heptyl group, octyl group, decyl group and dodecyl group.
The xe2x80x9chalogen atomxe2x80x9d refers to a chlorine atom, bromine atom, iodine atom or fluorine atom. The xe2x80x9chalo-(C1-12)alkyl groupxe2x80x9d refers to a linear or branched alkyl group having 1-12 carbon atoms of which one or more hydrogen atoms have been substituted with one or more halogen atoms which may be the same or different and may be, for example, the difluoromethyl group, trifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 3-chlorobutyl group, 3-bromobutyl group, 1-chloropentyl group, 1-chlorohexyl group, 6-bromohexyl group and bromododecyl group.
The xe2x80x9c(C3-8)cycloalkyl groupxe2x80x9d refers to a cyclic alkyl group having 3-8 carbon atoms and may be, for example, the cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. The xe2x80x9c(C1-3)alkyl(C3-8)cycloalkyl groupxe2x80x9d refers to a cycloalkyl group having 3-8 carbon atoms of which one or more of the hydrogen atoms have been substituted with one or more alkyl groups, which may be the same or different, selected from alkyl groups having 1-3 carbon atoms, e.g., the methyl group, ethyl group and isopropyl group.
The xe2x80x9c(C1-27)perfluoroalkyl groupxe2x80x9d refers to an alkyl group having 1-27 carbon atoms of which the entire hydrogen atoms have been substituted with fluorine atoms, wherein the alkyl may be either of a straight chain or branched chain or cyclic, which may be interrupted by an oxygen atom, and may be, for example, the trifluoromethyl group, n-pentafluoroethyl groups, n-heptafluoropropyl group, heptafluoroisopropyl group, n-nonafluorobutyl group, sec-nonafluorobutyl group, nonafluoroisobutyl group, undecafluoroneopentyl group, undecafluoropentyl group, tridecafluorohexyl group, pentacosafluorododecyl group, -A1-A2-D (wherein A1 represents (CF2), wherein l is an integer of 0 to 24, A2 represents (CFY)m, wherein Y is a fluorine atom or trifluoromethyl group and m is an integer of 0 or 1, and D represents the trifluoromethyl group), or 
wherein A3 and A4 may be the same or different and each represent xe2x80x94(CF2)nxe2x80x94CF3, wherein n is an integer of 0 to 15, or xe2x80x94(CF2)pO(CF2)qxe2x80x94CF3, wherein p and q may be the same or different and each denote an integer of 0 to 12, further, A3 and A4 may conjointly form xe2x80x94(CF2)rxe2x80x94, wherein r is an integer of 2 to 7, and E is a fluorine atom. When the number of carbon atoms is 2 to 27, examples of the perfluoroalkyl group include the perfluoroalkyl groups shown above other than the trifluoromethyl group.
When a group contains an xe2x80x9calkoxy groupxe2x80x9d or xe2x80x9calkoxyxe2x80x9d moiety, these terms mean a straight or branched chain alkoxy group. The xe2x80x9c(C1-6)alkoxy groupxe2x80x9d refers, for example, to the methoxy group, ethoxy group, isopropoxy group, sec-butoxy group, t-butoxy group, 1,2-dimethylpropoxy group and hexyloxy group. The xe2x80x9chalo(C1-6)alkoxy groupxe2x80x9d refers to a straight or branched chain alkoxy group of which one or more of the hydrogen atoms have been substituted with one or more halogen atoms which may be the same or different and may be, for example, the difluoromethoxy group, trifluoromethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 2,2,2-trifluoroethoxy group, 3-chlorobutoxy group, 3-bromobutoxy group, 1-chloropentyloxy group, 1-chlorohexyloxy group and 6-bromohexyloxy group.
The xe2x80x9c(C1-6)alkylthio groupxe2x80x9d refers, for example, to the methylthio group, ethylthio group, isopropylthio group, sec-butylthio group, t-butylthio group, 1,2-dimethyl-propylthio group and hexylthio group.
According to the process of the present invention, perfluoroalkylaniline derivatives can be obtained with a high position selectivity and high yield by using various anilines as the substrate. The process of the present invention makes it possible to use a catalytic amount of inexpensive reaction initiating agent and an easily recoverable reaction solvent which doubles as an extraction solvent, and further produces only a very small amount of wastes and hence is advantageous both environmentally and economically. Thus, the present invention provides novel perfluoroalkylaniline derivatives which have industrially versatile and valuable uses and a process for producing industrially valuable perfluoroalkylaniline derivatives, particularly secondary perfluoroalkylaniline derivatives.
A representative production process according to the present invention is described below, but the invention is not limited thereto. 
wherein R1, R2, R3xe2x80x2, R4xe2x80x2, R5xe2x80x2, R6xe2x80x2, R7xe2x80x2, R12, R13, R14, R15, R16 and R17 are as defined above.
The aniline derivative represented by the formula (Ixe2x80x2)can be produced by reacting an aniline represented by the formula (III) with an iodide represented by the formula (II) in the presence of a reaction initiating agent, in the presence or absence of a base and in the presence or absence of an inert solvent. The present reaction may also be conducted by using as an inert solvent water and a water-insoluble inert solvent and using a phase transfer catalyst.
The reaction of the production process 1 is described in detail below, but the present invention is not to be limited to those specifically exemplified hereunder.
1. Reaction Materials
(1) Iodide
The iodide represented by the formula (II) used in the present invention may be, for example, perfluoroethyl iodide, perfluoroisopropyl iodide, perfluoro-n-propyl iodide, perfluoro-sec-butyl iodide, perfluorocyclopentyl iodide and tetrafluoro-1-trifluoromethoxy-1-iodoethane. R12 is the formula (II) is preferably a secondary perfluoroalkyl group. Iodides whose perfluoroalkyl groups are of a long chain may also be used The reaction easily proceeds when the number of carbon atoms of the alkyl group is up to about 16.
(2) Anilines
Anilines represented by the formula (III) which may be used include, for example, aniline, fluoroaniline, chloroaniline, dichloroaniline, bromoaniline, 2-toluidine, 3-toluidine, 4-toluidine, 2-anisidine, 3,4-dimethoxyaniline, ethylaniline, isopropylaniline, 2-t-butylaniline, 2,6-dimethylaniline, N,N-dimethylaniline, 2,6-diethlaniline, N,N-diethylaniline, diisopropylaniline, 2-fluoro-3-methylaniline, 3-chloro-4-methylaniline, biphenylaniline, aminophenol, anisidine, ethoxyaniline, phenoxyaniline, dimethoxyaniline, phenylanisidine, phenylenediamine, methylthioaniline and N-methyltoluidine.
2. Reaction Initiating Agent
The reaction initiating agents which may be used include a reducing agent and light irradiation. The reducing agent may be, for example, dithionous acid salts, such as sodium dithionite and potassium dithionite, or zinc-aqueous sulfurous acid. The amount of the reducing agent is not particularly limited, but it is usually from about {fraction (1/100)} to about 2 equivalents, preferably in the range of {fraction (1/10)}-1.2 equivalents, relative to 1 equivalent of the reaction material (anilines). The light source used for irradiation with light is not particularly limited so long as it can provide a sufficient energy to initiate the reaction and may be, for example, a high pressure mercury lamp.
The reducing agent and light irradiation as the reaction initiating agent may be used either singly or in combination of the two.
3. Phase Transfer Catalyst
The phase transfer catalysts which may be used include, for example, quaternary ammonium salts, such as tetrabutylammonium hydrogen sulfate and tetrabutylammonium bromide, organic phosphorus salt compounds, such as tetrabutylphosphonium bromide, and alkylpolyether alkylamine compounds, such as tris (methoxyethoxyethyl)amine. The use of a phase transfer catalyst is not always necessary but in some cases gives better results. The amount of the catalyst to be used is not particularly limited, but it is usually from about {fraction (1/500)} to about 2 equivalents, preferably in the range from about {fraction (1/50)} to about 1 equivalent relative to 1 equivalent of the reaction material (anilines).
4. Base
The bases which may be used are inorganic bases and organic bases. The inorganic bases may be, for example, alkali metal carbonates, such as sodium hydrogen carbonate, sodium carbonate and potassium carbonate, and alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide. The organic bases may be, for example, triethylamine and 4-dimethylaminopyridine.
5. Inert Solvent
The inert solvent to be used is not particularly restricted so long as it does not markedly inhibit the progress of the reaction. It may be, for example, ether type solvents, such as diethylether, tetrahydrofuran, dioxane and t-butyl methyl ether, halogen-containing solvents, such as dichloroethane, inert benzene type solvents, such as nitrobenzene, ketone type solvents, such as acetone and cyclohexanone, ester type solvents, such as ethyl acetate, nitrile type solvents, such as acetonitrile and pivalonitrile, amide type solvents, such as dimethylformamide, and water. These inert solvents may be used each alone or as a mixture of two or more thereof.
Though depending also on the substituents of the raw material and the reaction conditions, the use of, for example, a nonpolar solvent as the inert solvent results, in many cases, in a good reaction selectivity and affords a more preferable reaction conditions. When a nonpolar solvent is used, the reaction system, as it is or, according to circumstances, with addition of a necessary amount of nonpolar solvent, can be subjected to an extraction operation; this is advantageous also in point of production cost.
When a phase transfer catalyst is used, the reaction may also be conducted in a two-phase system comprising a combination of water and a nonpolar solvent as the inert solvent. The inert solvent used can be selected as desired from the above-mentioned inert solvents, the use of a two phase system comprising water and an inert solvent yielding a good result.
6. Reaction Temperature
The reaction may be conducted at reaction temperatures approximately in the range from 0xc2x0 C. to the boiling point of the solvent at the reaction conditions. The reaction is preferably conducted at about 0xc2x0 C. to about 50xc2x0 C. with advantage in industrial production.
7. Reaction Time
The reaction time varies depending on the reaction conditions, but it is usually from several minutes to several tens of hours, preferably from about 30 minutes to about 24 hours.
In the present reaction, after completion of the reaction, the intended product is isolated from the reaction system by a conventional method and then, according to necessity, subjected to purification, etc., whereby the intended product can be produced.
The aniline derivative represented by the formula (I) can also be produced by first producing an aniline derivative wherein R1 and R2 are each a hydrogen atom according to the process of the present invention and then producing the intended derivative by a conventional method. For example, acylation by a reaction with an acid halide in the presence of a base, N-alkylation by a reaction with an alkylating agent or formylation using formic acid can be applied. Further, substituents may be introduced additonally onto the benzene ring. For example, an alkylaminomethyl group can be introduced, according to the method described in Russ. Chem. Rev., 46, 891-903, by haloalkylation conducted in the presence of formaldehyde, hydrochloric acid, catalyst, such as zinc chloride, and solvent, followed by reaction with an amine.